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Challenges and Advances
in Computational Chemistry and Physics 28
Series Editor: Jerzy Leszczynski
Nir Goldman Editor
Computational
Approaches
for Chemistry
Under Extreme
Conditions
Challenges and Advances in Computational
Chemistry and Physics
Volume 28
Series editor
Jerzy Leszczynski
Department of Chemistry and Biochemistry
Jackson State University, Jackson, MS, USA
This book series provides reviews on the most recent developments in computa-
tional chemistry and physics. It covers both the method developments and their
applications. Each volume consists of chapters devoted to the one research area.
The series highlights the most notable advances in applications of the computa-
tional methods. The volumes include nanotechnology, material sciences, molecular
biology, structures and bonding in molecular complexes, and atmospheric
chemistry. The authors are recruited from among the most prominent researchers
in their research areas. As computational chemistry and physics is one of the most
rapidly advancing scientific areas such timely overviews are desired by chemists,
physicists, molecular biologists and material scientists. The books are intended for
graduate students and researchers.
All contributions to edited volumes should undergo standard peer review to
ensure high scientific quality, while monographs should be reviewed by at least two
experts in the field. Submitted manuscripts will be reviewed and decided by the
series editor, Prof. Jerzy Leszczynski.
More information about this series at http://www.springer.com/series/6918

Nir Goldman
Editor
Computational Approaches
for Chemistry Under Extreme
Conditions
123
Editor
Nir Goldman
Materials Science Division
Lawrence Livermore National Laboratory
Livermore, CA, USA
ISSN 2542-4491 ISSN 2542-4483 (electronic)

Challenges and Advances in Computational Chemistry and Physics
ISBN 978-3-030-05599-8 ISBN 978-3-030-05600-1 (eBook)
https://doi.org/10.1007/978-3-030-05600-1
Library of Congress Control Number: 2018964691
© Springer Nature Switzerland AG 2019

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Preface
This book presents recently developed computational approaches for the study of
reactive materials under extreme conditions, with an emphasis on atomistic meth-
ods or those derived from atomistic calculations. Our intention is to include
state-of-the-art developments in a single source, spanning high pressures (e.g., 10s
to 100s of GPa), high temperatures (up to 1000s of degrees Kelvin), and even
strong electrical fields. The methods presented here include ab initio approaches
such as Density Functional Theory (DFT) and semi-empirical quantum simulation
methods (spanning nanometer length scales and picosecond timescales) as well as
reactive force field and coarse-grained approaches (spanning microns, nanoseconds,
and beyond). These approaches are readily applied across a broad range of fields,
including prebiotic chemistry in impacting comets, studies of planetary interiors,
high-pressure synthesis of new compounds, and detonations of energetic materials.
We have aimed to emphasize the strong connection with experiments throughout
the book. Our hope is that this will prove to be a useful reference for both com-
putational scientists wishing to learn more about specific subfields in this area as
well as experimental scientists wishing to gain familiarity with well-known com-
putational approaches for simulation of their experiments.
The book can be subdivided into a number of ways that will hopefully prove
instructive to both experts and the uninitiated. Broadly speaking, Chaps. 1–5 have
focused on some sort of quantum simulation approach, mainly with Kohn–
Sham DFT as the starting point. Chapters 1, 4, 6, 7, and 8 discuss force field
simulation and development for classical molecular dynamics calculations.
Chapters 8, 9, and 10 discuss coarse-graining approaches to extend prediction of
physical and chemical properties to closer to experimental time and length scales. In
more detail, Chap. 2 focuses on crystal composition and structure prediction
through evolutionary algorithms. Chapters 3 and 4 discuss semi-empirical quantum
method developments, which can yield significantly longer timescales for molec-
ular dynamics simulations while still providing information about electronic states.
Chapter 4 places an emphasis on refining both semi-empirical and classical
molecular dynamics simulations through force matching to DFT-MD trajectories,
v
vi Preface
including approaches for speeding up the fitting process through linear least-squares
fitting. Chapters 4, 5, and 6 discuss extending quantum simulations to long time-
scales through free energy calculations and accelerated simulation approaches.
Chapter 8 has some focus on novel reactive coarse-graining approaches for
shock-induced volume collapsing reactions. Chapters 9 and 10 place additional
emphasis on use of machine-learning methods to extend physical–chemical simu-
lation approaches to closer experimental time and length scales.
The chapters in this book can also be neatly subdivided by application area.
Chapter 1 discusses hydrocarbon polymers under extremely high pressures and
temperatures. Chapters 2, 8, and 10 explore energetic materials, with Chaps. 8 and
10 exploring reactive conditions. Chapters 4, 5, and 6 explore prebiotic chemistry,
and the role extreme conditions can play in the synthesis of simple, life-building
precursors. Chapters 3 and 8 focus on the chemistry of simple organics under shock
compression conditions. Chapter 9 investigates the reactivity of jet fuels under
combustion (high temperature) conditions.
Ultimately, we wish for this volume to be a useful pedagogical tool for a wide
variety of researchers in extreme physics and chemistry. Though our specific
emphasis has been on elevated conditions, the work presented here can be gener-
alized very easily to other materials, pressures, and temperatures. Our collective
efforts can be broadly applied to any number of scientific efforts spanning many
different types of compounds and reactive conditions. Thus, the aim for our book is
to be impactful for any research area that relies on atomistic simulation approaches
to guide and elucidate experimental studies and materials discovery.
Livermore, USA Nir Goldman

October 2018
Contents
1 Simulations of Hydrocarbon Polymers Related to Compression

Experiments on Sandia’s Z Machine . . . . . . . . . . . . . . . . . . . . . . . . 1
Thomas R. Mattsson, Kyle R. Cochrane, J. Matthew D. Lane
and Seth Root
2 Computational Discovery of New High-Nitrogen Energetic
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Brad A. Steele and Ivan I. Oleynik
3 Accelerated Molecular Dynamics Simulations of Shock-Induced
Chemistry: Application to Liquid Benzene . . . . . . . . . . . . . . . . . . . 53
E. Martínez, E. M. Kober and M. J. Cawkwell
4 Force Matching Approaches to Extend Density Functional
Theory to Large Time and Length Scales . . . . . . . . . . . . . . . . . . . . 71
Rebecca K. Lindsey, Matthew P. Kroonblawd, Laurence E. Fried
and Nir Goldman
5 Free Energy Calculations of Electric Field-Induced Chemistry . . . . 95
Giuseppe Cassone, Fabio Pietrucci, Franz Saija and A. Marco Saitta
6 Force Field Development and Nanoreactor Chemistry . . . . . . . . . . 127
Lee-Ping Wang
7 Application of ReaxFF-Reactive Molecular Dynamics
and Continuum Methods in High-Temperature/Pressure
Pyrolysis of Fuel Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
Chowdhury Ashraf, Sharmin Shabnam, Yuan Xuan
and Adri C. T. van Duin
8 Shock-Induced Chemistry: Molecular Dynamics and Coarse
Grain Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Md Mahbubul Islam, Mathew Cherukara, Edwin Antillon
and Alejandro Strachan
vii
viii Contents
9 Data-Driven Methods for Building Reduced Kinetic Monte

Carlo Models of Complex Chemistry from Molecular
Dynamics Simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
Qian Yang, Carlos A. Sing-Long, Enze Chen and Evan J. Reed
10 Toward a Predictive Hierarchical Multiscale Modeling
Approach for Energetic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . 229
Brian C. Barnes, John K. Brennan, Edward F. C. Byrd,
Sergei Izvekov, James P. Larentzos and Betsy M. Rice
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
Chapter 1
Simulations of Hydrocarbon Polymers
Related to Compression Experiments
on Sandia’s Z Machine
Thomas R. Mattsson, Kyle R. Cochrane, J. Matthew D. Lane and Seth Root
Abstract High-fidelity modeling of hydrocarbon polymers is important for gaining

fundamental understanding of the underlying material behavior as well as for design-
ing high energy density (HED) experiments. In this chapter, we describe multi-scale
modeling/simulation of hydrocarbon polymers done at Sandia and corresponding
experiments on Sandia’s Z machine. For polymers, a combination of first-principles
simulations using density functional theory (DFT) and atomistic simulations using
classical molecular dynamics has proven to effectively model different aspects of
the system and we will present both. Throughout, we find that the simulations are
in qualitative and quantitative agreement with experiments, suggesting that the hier-
archy of simulations can be used to increase our understanding of polymers under
dynamic loading conditions.
1.1 Introduction
Hydrocarbon polymers are versatile and therefore ubiquitous materials in experimen-

tal loads on high energy density (HED) facilities like the National Ignition Facility
(NIF), the Omega laser facility at Laboratory for Laser Energetics (LLE), and the
Z machine at Sandia National Laboratories. The physics of polymers span large
length- and timescales and the way of modeling polymers has to change to match
the different physics. For example, under successively stronger shock compression,
polymers melt and dissociate into a hydrogen and carbon fluid/dense plasma. For
strong shocks, an accurate modeling of atomic dissociation is important, suggesting
that atomistic simulations based on quantum mechanics are the appropriate approach.
Polymers are also the building blocks of different types of foams, which have poros-
ity and other internal structure. Foams are extensively used to tailor the behavior in
high-pressure experiments not only on a pulsed power driver like the Z machine [41]
but also on laser drivers [45]. For foams, an additional scale enters, the scale of pores.
T. R. Mattsson (B) · K. R. Cochrane · J. M. D. Lane · S. Root

Sandia National Laboratories, Albuquerque, NM 87185, USA
e-mail: trmatts@sandia.gov
© Springer Nature Switzerland AG 2019 1

N. Goldman (ed.), Computational Approaches for Chemistry Under Extreme
Conditions, Challenges and Advances in Computational Chemistry and Physics 28,
https://doi.org/10.1007/978-3-030-05600-1_1
2 T. R. Mattsson et al.
For foams, the use of classical molecular dynamics (MD) simulations using reactive
force fields has given new insights into formation of hotspots and other aspects of
shock dynamics in heterogeneous materials.
The outline of the chapter is as follows. The first section is a discussion on
first-principles simulations using density functional theory (DFT), including post-
processing to analyze the chemical composition of the material. The second section
presents classical MD simulations of hydrocarbon polymers and—foams, we show
how the shock propagates in the foam and how local hotspots are formed. In the third
section, we discuss Z experimental results on PMP plastic and demonstrate how Z
and simulations give a complete picture of the PMP shock response. The chapter
concludes with a summary and conclusions.
1.2 First-Principles Simulations of Shocked Polymers
First-principles simulations using Density Functional Theory have brought important

insights into how matter behaves under extreme conditions and, importantly, key pre-
dictions of thermodynamic properties from DFT simulations have been confirmed
experimentally. For example, Sandia’s Z machine has been employed to experi-
mentally determine the shock Hugoniot of a number of elements and compounds,
including carbon/diamond [25], xenon [47], water [28], carbon dioxide [48], hydro-
gen [23, 26], krypton [39], and quartz [27]. For these elements and compounds,
DFT simulations have been shown to predict the behavior with high fidelity. The
DFT modeling of shock compression of hydrogen, carbon, water, carbon dioxide
strongly suggests that it is possible to use DFT to successfully simulate hydrocarbon
polymers as well. That said, polymers add complexity and the excellent agreement
between DFT simulations and experiments demonstrated in 2015 [50] was far from
a foregone conclusion.
Density functional theory is based on a theoretical discovery by Walter Kohn [18,
29] that the energy of the electron gas of N electrons can be formulated as a functional
of the electron density in real space (3 spatial coordinates) without an explicit use
of the wave functions (3 N spatial coordinates, one for each electron). The resulting
simplification is tremendous since the problem is reduced from 3 N dimension to 3.
The discovery soon resulted in practical quantum simulations of electronic structures
of solids, atoms, and molecules. The field has expanded, and DFT simulations are now
commonplace across physics, chemistry, biology, and materials science. Although
a review of applications of DFT is well outside the scope of this chapter, we will
discuss the most important factors of applying DFT to high energy density conditions
in general and post-processing for polymers in particular. For a more thorough review
on designing DFT calculations for materials science, including HED, please see [37].
1 Simulations of Hydrocarbon Polymers Related … 3
1.2.1 First-Principles Thermodynamics of Shock

Compression
DFT is applied to problems in physics, material science, and chemistry to calculate

the energy in atomic systems. DFT calculations are used to compare energy differ-
ences between structures and determine energy barriers between transitions. One of
the most common DFT calculations is ionic position optimizations to minimize the
system energy and to determine transition paths in the energy landscape. The elec-
tronic structure is mostly sought for the lowest, zero Kelvin, energy state, where the
Fermi distribution is a step function. The discontinuous Fermi distribution requires
extensive k-point sampling of reciprocal space in order to capture the behavior well.
Shock compression, on the other hand, involves a discontinuous jump from an initial
state to a final state that often is at very high temperature (Fig. 1.1).
Shock physics is driven by the Rankine–Hugoniot (RH) jump conditions, which
link the initial and final states for a system with a propagating shock wave of speed
us and particle velocity after the shock up . The RH equations are derived from the
conservation of mass, momentum, and energy across the front discontinuity:
(P2 − P1 ) ρ1 (u s − u 1 )(u 2 − u 1 ) (1.1)
ρ2/ ρ1 (u s − u 1 )/(u s − u 2 ) (1.2)
1
(e2 − e1 ) (P2 + P1 )(v1 − v2 ) (1.3)
2
where e is the specific internal energy, P is pressure, and ρ is the density. The
subscripts 1 and 2 designate the initial and final states, respectively. The result is a
thermodynamics relationship between pressure, specific volume (v 1/ρ), and inter-
nal energy of the final and initial states, the so-called Rankine–Hugoniot relationship
(1.3) [6].
us
u2 u1
2 1
Fig. 1.1 Shock wave in a material, the shock is supersonic and causes a discontinuous transition
from thermodynamic state 1 to state 2. The shock velocity is us and the net particle velocities before
and after the shock are u1 and u2 . The initial and final states are linked by conservation laws. The
analysis can, for example, be made as a thermodynamic control volume
Fig. 1.2 The end states of shock compression of polyethylene [9] (black) and three release paths
from different initial shock pressures. Note the shoulder in the Hugoniot between 100 and 150
GPa caused by dissociation of the polymer. Above 150 GPa, there are no longer any molecular
fragments, see Fig. 1.7
In thermodynamic space, the loci of end states generated from successively

stronger shocks starting from a common initial state are called the Hugoniot.
Figure 1.2 shows the polyethylene Hugoniot in density–temperature space (ρ–T )
and pressure–temperature (P–T ). Figure 1.2 also shows release isentropes: the path
the initial shock state relaxes from when the driving pressure is released. Note that the
RH equations do not depend on the temperature except via the internal energy. Tem-
perature is extremely difficult to measure experimentally, so there is more uncertainty
involving temperature than pressure and density.
The RH energy relationship points toward the need for high accuracy calculations
of internal energy and pressure in simulations of shock compression. It is evident that
temperature plays a key role, making molecular dynamics (MD) simulations appro-
priate for sampling the thermodynamics ensemble [1]. At the high temperatures of
shock compression, MD is a highly efficient method of sampling the thermodynamic
phase space [1].
Importantly, temperature also affects the electronic structure making it necessary
to use the Mermin finite-temperature formulation of DFT [42] which involves cal-
culating the full Fermi distribution of electronic states. At high temperature, the full
Fermi distribution includes many partially occupied continuum states, requiring sig-
nificantly more electronic bands than a normal “cold” DFT calculation does. The
consistent use of finite-temperature DFT is one of the most important aspects of
performing high-fidelity simulation in the HED regime.
While the thermal–structural disorder at high temperature relaxes the demands
for using a dense k-point sampling compared to that required for calculations of
ordered solids at zero Kelvin, it is necessary to apply a high plane-wave cutoff
energy in order to converge the electronic pressure [37]. The pressure is calculated
with derivatives of the electronic structure and hence converges more slowly than the
internal energy. The use of finite-temperature and systematic convergence were two
main reasons behind the first high-precision calculations of the deuterium Hugoniot
[11]. To summarize, DFT-based molecular dynamics calculations, often referred
to as QMD—quantum molecular dynamics—of shock compression requires high
Fig. 1.3 Obtaining thermodynamic information from a long MD simulation. The moving average
is a useful measure for when the periodic oscillations in the simulation no longer influence the
result. A drift toward lower pressure during the simulation, for example, would indicate relaxation
in the system and a longer simulation time is needed
plane-wave cutoff energies, finite-temperature DFT using many partially occupied

bands, and the use of pseudo-potentials that are of high quality for normal conditions
as well as high-pressure and high-temperature conditions.
Figure 1.3 shows the electronic pressure for a polystyrene simulation at 1.05 g/cc
and 300 K. The time step is 0.5 fs. The red line is the moving average of the pressure
and is strongly influenced by the correlation between atom positions. In this plot, the
initial time for starting the moving average was picked to be close to the estimated
mean pressure, so, while the mean of the electronic pressure is 0.67 ± 0.015 GPa,
this is misleading as picking a different starting position will yield the same standard
deviation but a different mean until many more time steps. Block averaging is a
powerful way of extracting uncertainties from correlated data [1]. In this case, the
block size used was 37 but made little difference between 20 and 45. The block
averaged mean is 0.70 ± 0.08 GPa.
1.2.2 Analysis of Chemical Composition—Tracking Bonds
Of particular importance to simulation of polymers compared to elements is the pres-

ence of covalent bonds and the energy associated with bond breaking. The breaking
of covalent bonds takes energy, energy that otherwise would be available for increas-
ing the temperature of the shocked material. The result on the Hugoniot curve is the
shoulder in temperature evident in Fig. 1.2 at 2.25 g/cm3 / 120 GPa. In this section, we
present a way of identifying molecular structure and apply it to conditions commonly
created by strong shock waves in polymer systems.
Fig. 1.4 Species-dependent pair correlation function for ethane at 0.571 g/cm3 and 300 K. The
pair correlation plateaus at 1.00 since the pair correlation function is normalized to the random
probability of finding an atom in space, hence without any correlation the value is 1.00
Tracking bonds in a simulation is a three-step process. We determine bond lengths,

determine bond times, and then, based on those lengths and times, identify and track
the bonded atoms. Atoms are considered bonded if they stay within a given distance
of each other for a defined amount of time. If, at any time, one of the atoms drifts
outside of the prescribed distance and then drifts back in, the time is reset to zero
and must again be satisfied.
To determine bond length, we use the species-dependent pair correlation function
g(r) to find the distribution of distances between atoms in the reference system,
usually at ambient density and temperature. Figure 1.4 shows the pair correlation
function of carbon to carbon, carbon to hydrogen, and hydrogen to hydrogen for
ethane at 0.571 g/cm3 and 300 K. These simulations are several picoseconds long,
so we use multiple averaging times to obtain different samplings which allow us to
check that we do not have a large variation between each averaging time. We then
use these values in the bond tracking method on the reference system to confirm that
it yields the species of the initial state. Because we use a finite time step and have a
small number of atoms, we find that first minimum of the pair correlation for each
species is the best choice for bond lengths.
For the following example, we incremented the density of ethane from 0.6 to
4.0 g/cm3 by 0.1 g/cm3 and equilibrated each simulation at that density and constant
temperature in order to map out the Hugoniot locus points. When the Hugoniot
developed a slope inflection, which is often indicative of the onset of dissociation,
we calculated the pair correlation on the simulation just prior to the inflection density
to confirm that the molecules were still intact. This can be seen in Fig. 1.5. The
carbon–carbon bond length is the same. However, the carbon–hydrogen bond is
slightly longer, changing from 1.19 to 1.28 Å. Because these values are taken from
simulations closer to the dissociation regime in question, these are the values that
would be used for the bond tracking.
Fig. 1.5 Species-dependent

pair correlation function for
ethane at 1.2 g/cm3 and
1050 K. The probability
approaches the random value
1.00 at a shorter
distance—reflecting less
correlation in the positions of
atoms than at lower
temperature
The next step is to determine the amount of time atoms must be in close proximity
to each other to be considered bonded. To start, we run the tracker on the simulation
in question and vary the C–C bond distance, C–H bond distance, H–H bond distance,
and time requirement.
At 1.5 g/cm3 , 3100 K, we varied the required bond lengths and times in order to
determine that there is no sensitive dependence on a particular cutoff parameter. The
results from this sensitivity study are shown in Fig. 1.6. The hydrogen–hydrogen is not
shown as it made no difference. Each plot uses different carbon–carbon bond lengths,
varied between 1.60 and 1.72 Å. The abscissa is the carbon–hydrogen bond length
and is the same for all figures. Finally, the different colored lines denote different
proximity time requirements from 60 to 120 fs. In a transient system such as this,
as time goes to infinity, we expect the free carbon and free hydrogen to approach
their atomic ratios (carbon to 33% and hydrogen to 66%). It can also be seen that
there appear to be no clear breakpoints for picking one bond distance over another,
hence using the pair correlation functions as a guide. If there were distinct features
in Fig. 1.6, we would need to investigate the cause for them before continuing.
We use atom velocity as a guide to select a suitable duration. For this example,
we used the kinetic theory of gasses and ideal gas law as a crude approximation to
the velocity.
1 2 3
mv kB T
2 2
where k B is the Boltzmann’s constant, T is the absolute temperature, m is the mass
(in our case of a single atom), and v is the average Maxwellian velocity. With T
3100 K, for carbon, we get a velocity of 2538 m/s or 0.02538 Å/fs. Therefore, over
100 fs, we can expect a single atom to move about 2.5 Å. For hydrogen, this would
be about 25 Å. We assume that for C–H, the atoms must be bonded if the hydrogen
does not rapidly move away from the carbon. Similarly, unless both carbons are
moving parallel, they would still drift apart quickly enough to fail the time/distance
Fig. 1.6 Change in perceived composition as a function of bond distances for ethane at 1.5 g/cm3
and 3100 K. The changes are smooth, so the selection of a particular bond cutoff does not change
qualitative behavior
constraint. We use the vibrational period as a reference for our bond time calculation.
A carbon–carbon triple bond has a full period of about 18 fs. For a double bond such
as ethylene, the period is about 21 fs, and the period for a single bond in ethane
is about 33 fs. The 100 fs time cutoff was chosen to be significantly longer than
multiple vibration periods. The tracking method has a hard reset to a given molecule
interaction meaning if two atoms move apart farther than the distance cutoff, they
must satisfy the distance constraint for the entire time constraint again before they are
considered bonded. This allows us to better distinguish between a scattering event
and a bond.
After identifying all of the bonded atoms, we can begin to identify molecules. Our
method uses a recursive algorithm capable of identifying branched molecules beyond
a nearest-neighbor picture. One way to conceptualize this information is by building
a three-dimensional construct where the first two dimensions are a matrix of atom-
to-atom bonds (designated by either a 0 or 1 but more information can be stored)
and the third dimension is time. The algorithm walks through the time-dependent
upper diagonal, following all bonded pairs until no more bonds are found in that
chain (at which point it starts with the next atom not in that chain) or until all atoms
are accounted for.
The recursive nature of the algorithm makes it fast and reliable. The ability of
looking beyond nearest neighbor is particularly important for the purpose of changing
chemistry. In the case of polyethylene, the polymer structure is never recovered if
cooled, but other species may be formed which helps us to understand how the
system evolves from a metastable polymer to thermodynamic equilibrium along a
given trajectory in a phase diagram.
Figure 1.7 shows the stoichiometry for four strands of polyethylene along the
principle Hugoniot calculated according to the method described above. This series
of simulations was performed with four strands of CH2 , 16 carbon atoms long and
with an extra hydrogen atom at each end to cap the chain and prevent cross bonding
(for a total of 200 atoms). For densities of 1.1 to 1.7 g/cm3 , all four strands are intact.
At 2.6 g/cm3 , the system is almost entirely an atomic gas. Between 1.7 and 2.7 g/cm3
is the dissociation regime responsible for the inflection in the Hugoniot. Outside of
this regime, the stoichiometry is easy to calculate, but inside the variety and species of
molecules is much harder to understand and additional constraints are often required,
not on the bond tracking program itself but on the results. For example, one might
Fig. 1.7 Polyethylene stoichiometry along the principal Hugoniot. These simulations used 4 strands
of 16 carbons and 32 hydrogens along the chain plus 2 hydrogens (one at each end) to cap the strand
and prevent cross bonding. 1.1 g/cm3 through 1.7 g/cm3 show only C16 H34 which indicates that all
four strands are intact. At 2.6 g/cm3 the system is almost entirely an atomic gas
see a C1 and C7 H5 for a few time steps and then see a C2 and C6 H5 for a few time
steps. These are transients that do exist but are difficult to quantify in a meaningful
way given the very small number of atoms present in a DFT simulation. Figure 1.7
shows only the most persistent of the species.
With this tool, we are able to carefully follow the dynamic chemistry of poly-
mer dissociation as a function of shock strength. Accurate accounting of species is
important for understanding the role of bond breaking in release of internal energy,
for comparisons with classical molecular dynamics simulations using reactive force
fields, and for comparison with chemical reactivity models.
1.3 Classical Molecular Dynamics Simulations of Polymers

Under Shock Compression
DFT allows extremely high-fidelity descriptions of chemistry over a huge range of

compressions; however, its system sizes are computationally constrained to just a few
hundred atoms. This can be a significant obstacle, particularly in polymeric systems,
where even single chains can easily exceed this number of atoms. Furthermore, in
the case of structured polymers and foams, nanoscale features cannot be captured
on length scales available to DFT. Thus, for the study of void collapse and hotspot
heating, another simulation tool is required.
Classical molecular dynamics (MD) can extend the accessible simulation length
scales to tens or hundreds of nanometers (and many millions to billions of atoms),
by eliminating the electronic degrees of freedom and reducing quantum mechanical
interactions into a classical ion–ion interatomic potential. These potentials are gen-
erally quantitatively accurate over smaller compression ranges than DFT, but can be
highly accurate within these ranges.
Our classical MD simulations are run with Sandia’s LAMMPS parallel molecular
dynamics code [44]. LAMMPS allows highly efficient large-scale calculation and
offers a broad library of established interaction potentials. For hydrocarbons, we have
taken advantage of this library to compare the shock response of several published
potentials under identical loading conditions.
In Mattsson et al. [38], we compared the results of two reactive and two bonded
interatomic potentials. The reactive force fields, ReaxFF [7] and AIREBO [53] allow
for chemical reactions and dissociation. The bonded force fields, OPLS-AA [21] and
the Borodin et al. exponential-6 [4, 5] are computationally much more efficient but
cannot capture dissociation reactions.
It had been expected that the reactive potentials would do better than the less
sophisticated bonded potentials. However, we found that core stiffness was a stronger
predictor of a potential’s accuracy than its reactivity. Specifically, we found that the
AIREBO and OPLS potentials were both too stiff in compression, and diverged from
DFT and experiments well before the onset of dissociation chemistry. Since our 2010
study, however, both the AIREBO and OPLS potentials have been reworked to sig-
nificantly address the observed shortcomings in their high compression response.

AIREBO-M [43] was refit to high-pressure graphene and polyethylene data, and
now reproduces DFT results for shocked PE at least up to 40 GPa. Similarly,
Sewell, Frohlich, and Thompson [13] showed how OPLS-AA can be refit to use
exp-6 Buckingham-style interactions to replace the stiffer 12–6 Lennard-Jones cores.
Given these improvements since our last comparison, we focus our discussion on the
ReaxFF and Borodin potentials.
Shock compression states were produced using two MD methodologies. In the
case of homogeneous full-dense polymer studies, the Hugoniostat [46] method was
used to homogeneously bring the material to the final shock state. This equilibrium
approach uses modified equations of motion to correlate the system compression to
the internal energy thermostat, so as to enforce the RH relation, (1.3). For shocked
foams, we used a full nonequilibrium (NEMD) propagating wave approach [20,
22] in order to capture the nonuniform dynamical collapse around the void spaces.
NEMD uses a piston driver on one end of the system, to provide a sustained drive
into the sample, producing a shock front, which then propagates across the system.
Three representative ambient-density polymer systems are shown in Fig. 1.8. For
these studies, we built polymeric systems from either polyethylene (PE) or poly(4-
methyl 1-pentene) (PMP). While both materials have the same monomer C:H ratio
of 1:2, and nearly identical local structure, they differ in extended structure. PE
has a linear backbone, while PMP has a branched structure. Full-density systems
for PE (0.930 g/cm3 , Fig. 1.8a), and PMP (0.801 g/cm3 , Fig. 1.8b) were built and
equilibrated. In addition, the amorphous PMP was conducive to building distended
foam systems (0.30 g/cm3 , Fig. 1.8c) as well. Details of the building and equilibration
have been published [38, 49].
Figure 1.9 shows two plots of polymer Hugoniot response from Z experiments,
DFT, and MD simulations. The MD simulations shown are for the ReaxFF and
Borodin et al. potentials. We note that DFT best reproduces experiments over the full
range of compression. The MD does reasonably well at lower compression but is gen-
erally stiffer than experimental measurements as pressure increases. In both the PE
and PMP, the ReaxFF potential gives the better agreement with experiment between
the two MD potentials shown. To within experimental uncertainty, it is accurate from
ambient density up to approximately 2× ambient density. The Borodin potential is
good from ambient up to ~1.6 g/cm3 . Moreover, the ReaxFF potential shows good
agreement with DFT dissociation onset, as shown in Fig. 1.10, which begins at just
above 1.8 g/cm3 (vertical dashed line) in polyethylene. Figure 1.10 plots the percent-
age of carbon atoms bonded to two other carbons as a function of compression. This
simple measure of polymer chemistry shows agreement between DFT and ReaxFF
MD in both onset density and density trend to complete vaporization.
Based on Hugoniot response and dissociation, we conclude that MD with the
ReaxFF potential gives comparable quantitatively accurate hydrocarbon simulations
to DFT under compression up to ~1.8 g/cm3 . This validation allows us to extend
atomistic simulations to length scales which are amenable to study of nanoscale
foams.
Fig. 1.8 Snapshots from initial configurations of molecular dynamics simulations for semicrys-
talline polyethylene (top left), poly(4-methyl 1-pentene), i.e., PMP (top right), and a model PMP
foam with density of 0.30 g/cm3 (bottom)
Fig. 1.9 Classical molecular dynamics Hugoniot response compared to experiments [36] and DFT
data for full-density polyethylene (left) and Poly(4-methyl 1-pentene) (right) [38]
Fig. 1.10 Dissociation, as percent carbon chain, for DFT (20 and 50 fs bond criteria are blue and
red, respectively) and ReaxFF classical MD (green) [38]. Maximum percent fraction is 87.5% for
the C16 polyethylene chains, and 95% for the C44 chains, shown
While foams and porous materials are frequently useful and necessary in shaping
high-pressure waves, their response is notoriously difficult to characterize. Experi-
mental error bars are usually large due to sample-to-sample foam variation, as well
as to inhomogeneities within individual samples. Issues of sample control combined
with a lack of direct experimental measures of temperature and chemistry make anal-
ysis difficult. Root et al. conducted Z machine shock experiments on PMP foams
with average density of 0.3 g/cm3 [49]. The experimental results were published with
extensive atomistic, and continuum simulations exploring the effects of porosity on
average temperature, vaporization/ejecta, and wave propagation profiles. Subsequent
work [30, 31] explored the temporal evolution of void collapse and local temperature
hotspot formation.
A foam Hugoniot comparison between Z machine experiments, MD simulation,
and Equation of State (EOS) calculations are shown in Fig. 1.11a. These results show
that the final densities of these compressed systems do not reach nearly the com-
paction that the fully dense polymer samples reach these pressures. This is because
the void collapse in foams leads to significant heating, which causes expansion in
the final states. Because of this, we remain well within the density range for which
ReaxFF has been shown to be reliable.
The Hugoniot curves for PMP foam have two distinct regions. At low pressures,
the foam compacts to approximately four times its initial density, at which point
the curve turns steeply vertical, with little increased density for large increases in
pressure. In both the EOS calculations and the MD simulations, the data is tightly
aligned along near-vertical lines. The experimental data, colored to match the same
initial densities of MD and EOS data, have significant horizontal variation. The
simulations help to build confidence for this being due to variation in foam density
across different samples.
Fig. 1.11 Comparison of the shock Hugoniot from classical MD and experiments on Z [48, 49].
Equation of state results are also shown for SESAME 7171 [12, 19]
Figure 1.11b shows the final average temperatures for the same shot data. Exper-
imental temperatures are not available. The data shows the strong dependence of
final temperature on the initial density of the foam. The fully dense polymer tem-
peratures are almost an order of magnitude lower than the foams. And the slope of
increased temperature with pressure increases with decreasing initial density. This
is consistent with the conclusion that increased void size/number leads to increasing
hotspots and higher temperatures. One also sees in the plots that the MD tempera-
tures show the same trends as the EOS temperatures and agree at lower pressures.
However, at higher pressures, the SESAME 7171 values are consistently lower than
MD temperatures, even when the pressure vs. density values agree. This is likely a
result of the fact that the EOS model does not account for the polymer dissociation,
which would indicate that the MD temperatures are more dependable. It should,
however, be noted that these temperatures are well above the range usually explored
with classical molecular dynamics.
The molecular dynamics snapshots in Fig. 1.12 demonstrate one significant mech-
anism, which was not observed in full-density polymer shock studies. We see sig-
nificant vaporization and ejecta within the collapsing void. This vaporized material
is produced at pressures and densities well below the onset of dissociation in dense
polymer, because the temperatures in the collapsing voids are high enough to break
bonds. Once the material is volatized, it can travel ballistically ahead of the shock
front. In closed foams, these ejected particles impact the far side of the void, pre-
heating the un-shocked material. In an open foam, the vaporized particles can travel
far ahead of the shock front through the interconnected void space. The ejected par-
ticles travel at velocities as high as twice the bulk particle velocity. This observation
explains features seen in the wave profiles. In both simulation and experiment, shock
fronts are broader than expected, and the rise time of the front appears to be correlated
to the void size.
These results indicate that classical molecular dynamics can be used effectively
to model Z machine experiments in polymer shock compression. Specifically, with
the right potentials, quantitative agreement can be made with DFT and experimental
Fig. 1.12 Snapshots of a propagating shock front showing vaporized ejecta from the collapsing
void. Atoms are colored by velocity in the shock direction. (left) piston velocity of 10 km/s, giving
pressure of ~40 GPa (right), piston velocity of 25 km/s, giving pressure of ~240 GPa. Dissociated
polymer is seen extending ahead of the shock front [31]
results over a useful range of compression. Moreover, because MD allows for the
simulation of much larger features than those which can be captured with DFT, it
can explore the mechanisms and processes associated with larger length scale struc-
ture in polymers (i.e., long-range order, defects, or voids). Moreover, aspects of the
compression which are difficult or impossible to observe experimentally, including
void collapse and temperature production, are readily studied with MD. For these
reasons, classical molecular dynamics has proven to be a useful tool to augment our
analysis and understanding of Z machine experiments.
1.4 Z Experiments on Polymer Materials
In the 1990s, Sandia researchers developed the Z machine as a pulsed power source
for generating X-rays for radiation–material interaction studies and as an X-ray drive
for experiments relevant for inertial confinement fusion studies [40, 52]. In 2007,
the Z machine was refurbished [51] increasing the maximum current delivered to a
target to approximately 20 MA in a pulse length of 100–600 ns making Z capable of
producing magnetic pressures up to 600 GPa. Early on, researchers [15] determined
that the current pulse could be used to drive a smoothly increasing compression
wave into a target load where the time-dependent magnitude of the pressure loading
is given as
B 2 (t) J 2 (t) μ0 I 2 (t)

P(t) μ0
2μ0 2 2W (t)2
Fig. 1.13 Illustration of the current drive on the anode. The magnetic field penetrates only a fraction
of the flyer, the shockless compression front outruns the magnetic field
where P is the pressure, B(t) is the time-dependent magnetic field, J(t) is the time-
dependent current density in units of (amps/unit length), I(t) is the time-dependent
current, and W (t) is a time-dependent scaling factor that depends on the load geom-
etry. This led to the first shockless compression experiments to measure quasi-
isentropes in materials [15]. From prior work at Sandia on the hyper-velocity launcher
(HVL) gun using a shockless compression wave to launch flyer plates [8], the idea
to use the Z machine to launch flyer plates was quickly conceived [16, 24].
Figure 1.13 shows the basic concept for either shockless compression or flyer plate
experiments on Z. Current is driven in a loop along the anode and cathode through a
shorting cap on the target’s top. This current loop generates a magnetic field between
the cathode and the anode. The combination of current and magnetic field creates a
Lorentz force ( F J × B) that drives a shockless compression wave through the
anode. A sample directly mounted to the anode will be shocklessly compressed as
the compression wave transits into it. If the anode is left with a free surface, just as
in the HVL, when the shockless compression wave reaches the anode free surface,
the anode is accelerated outward from the cathode. Using a shockless compression
wave minimizes the temperature rise in the anode, however, the high current causes
Joule heating on the inner surface of the anode. This causes the conductivity to drop
and the current begins to diffuse into the anode, which creates a magnetic diffusion
front that propagates behind the compression wave front. The Joule heating melts
and vaporizes the inner surface of the anode [10].
Fig. 1.14 Illustration of a Z coaxial geometry flyer plate experiment. The load is about 5 cm tall
and 1 cm wide
The ability to shape the current pulse along with developments in 1D and 2D
magnetohydrodynamics (MHD) simulations greatly improved the capabilities to use
the Z machine for quasi-isentropic compression experiments [10] and for flyer plate
experiments [32, 33]. By proper tailoring of the current pulse, the flyer plate is
shocklessly accelerated to the desired velocity. Experiments are designed to ensure
a steady shock through the sample and to avoid contamination in the measurement
from release waves reflecting from Joule heated, melted portion of the flyer. Fur-
ther refinements to the Z target geometry and improvements in MHD and Z circuit
modeling have led to the successful launching of aluminum flyer plates up to around
40 km/s [34].
Figure 1.14 illustrates a rectangular target geometry used for flyer plate experi-
ments. In this geometry, rectangular flyer plates are placed on opposite sides of the
cathode. The flyer plates are typically aluminum, but Z has also used Al/Cu layered
flyers where Cu is the impactor. The distance between the flyer plates and cathode,
called the AK gap, is asymmetric—one side has a larger AK gap than the other
side. This results in two different magnetic pressures that create two different flyer
velocities on each side of the target, and thus, two different Hugoniot states in one
experiment. MHD simulations are used to determine the flight gap so that the flyer
plate reaches a terminal velocity prior to impact with the samples with a few hundred
microns of solid density on the impact face [32, 33]. The target frame is designed to
hold as many samples as possible to maximize the data return.
The Z machine has been used to study the high-pressure response of the hydrocar-
bon polymer: poly(4-methyl-1-pentene) plastics up to 985 GPa [50]. Poly(4-methyl-
1-pentene) plastic (PMP) is a CH-based plastic in which the carbon atoms are sp3 -
hybridized. PMP is often referred to by its trade name TPX® (Mitsui Chemicals,
Inc.) and is available in several different variations. PMP is possible to machine and
is transparent, which makes it a valuable window material for shock-release studies
on the Z machine. For the work in [50], the PMP samples were the DX845 variant of
TPX® with a density of 0.833 g/cm3 and a melting temperature of 232 °C. The index
of refraction of PMP is relatively constant over a large range of wavelengths. For the
Z experiments, we use a 532 nm wavelength for our laser interferometry system. At
that wavelength, PMP has an index of 1.461 ± 0.001.
The laser interferometry system at Z is a velocity interferometer system for any
reflector (VISAR) that was originally developed at Sandia National Laboratories in
the late 1960s and early 1970s. Details of the VISAR technique for shock wave
research are found in [2, 3, 14, 17]. The VISAR measures flyer plate velocities and
shock velocities during the Z experiment.
Figure 1.15 shows a schematic illustration of the experimental configuration
along with two sample VISAR measurements. An aluminum flyer plate is accel-
erated toward the PMP samples. Two different sample configurations were used
for measuring the high-pressure response of PMP (inset): the top configuration is a
thick sample of PMP used to measure the Hugoniot. The bottom configuration is a
PMP/quartz window stack used to measure the Hugoniot and the reshock state in
PMP. In the experiment, VISAR tracks the flyer plate trajectory, directly measuring
the flyer plate velocity up to impact. The flyer plates are shocklessly accelerated
to the desired velocity. At impact, a shock is produced in the PMP sample. The
shock strength is high enough that the shock front in the PMP becomes reflective
and the VISAR laser reflects off the shock front. This allows for a direct, precise
measurement of the shock velocity as the shock wave travels through the sample.
Figure 1.15 (red) shows the shock through the PMP is steady for 10 s of ns. At
late times in the single PMP sample, the velocity begins to decrease. The velocity
decrease is caused by reflected release waves from the melted portion of the flyer
(Fig. 1.13). In the quartz backed PMP configuration, a steady wave is observed in
the quartz for 10 s of ns as well. At later times, a second shock is observed in the
quartz. This is caused by the reflected shock from the PMP/quartz interface and the
PMP/aluminum impactor interface. Again, release waves from the melted portion of
the flyer cause the decrease in the shock velocity.
The advantage to using the Z machine is that it launches solid density flyers at
the targets. Thus, the flyer plate is well characterized at impact. Combined with
the direct measurement of the shock velocity in the PMP, the Hugoniot state is
easily and accurately determined through impedance matching [6]. A Monte Carlo
impedance matching (MCIM) method [50] is used to calculate the Hugoniot state and
uncertainty. The MCIM method accounts for uncertainty in the measurements, initial
densities, and the uncertainty in the Hugoniot of the flyer plate. Figure 1.16 shows
the compiled Hugoniot data for PMP along with the QMD calculated Hugoniot for
PMP discussed earlier in the chapter.
Fig. 1.15 VISAR measured velocity traces from two different experiments on PMP plastics show-
ing the flyer velocity, PMP shock velocity, and the quartz shock velocity. Inset: Configuration for
experiments using the direct shock experiment (top sample) and the shock—reshock experiment
(bottom sample)
Fig. 1.16 Hugoniot of PMP plastic in density–pressure space. The left panel shows the low-pressure
range where there was previous data. The QMD simulations are in excellent agreement with data
over a large range
Figure 1.16 shows the Z experimental data range from 100 to 550 GPa along the
principal Hugoniot. The QMD calculations are in good agreement up to 400 GPa.
Starting at about 150 GPa, the principal Hugoniot steepens dramatically compared to
the Hugoniot below 100 GPa. The sharp upturn suggests dissociation of the molecular
system into an atomic system. This similar behavior along the Hugoniot was observed
in the molecular systems of CO2 [48, 49] and ethane (C2 H6 ) [35].
The bond tracking analysis method discussed earlier was used to assess dissocia-
tion along the Hugoniot. Figure 1.17 shows the results of the bond tracking analysis.
At low shock pressures of approximately 20 GPa, the polymer chain begins to break
Fig. 1.17 Analysis of the

atomic species of shocked
PMP using the bond tracking
analysis method
down and complex Cx Hy constituents are observed. Increasing the shock pressure
increased the amount of free hydrogen. At a shock pressure of approximately 150
GPa, all H atoms have dissociated from the C chains and the number of free C
atoms begins to increase. Complete dissociation into C and H atoms requires a shock
pressure of approximately 315 GPa.
At 315 GPa, the compression factor μ 1 − ρ0 /ρ is μ 0.68. At 160 GPa
where the system is primarily atomic C and H with a small percentage (~6%) of
C–C clusters, μ 0.66. Interestingly, this compression factor of μ 0.66–0.68
for complete dissociation is consistent with other C–H systems with sp3 -hybridized
bonded carbon. Complete dissociation for ethane (C2 H6 ) occurs at μ 0.69 [35],
for polyethylene μ 0.62 [9], and polystyrene μ 0.62 [54]. For each system, the
pressure and temperature at complete dissociation are different, but the compression
factors are all similar. This suggests that the C–C bonds are more affected by com-
pression than pressure or temperature since compression reduces the gap between
bonding and anti-bonding orbitals making it easier to occupy the anti-bonding states
in the C.
1.5 Summary and Conclusions
Hydrocarbon polymers are commonly used in shock physics research, and their
behavior is complex. Strong compression of hydrocarbon polymers involves a series
of physical mechanisms, together resulting in the Hugoniot response shown in
Fig. 1.2. Under progressively stronger shock loading, the hydrocarbon polymers dis-
cussed in this chapter (linear polyethylene and polymethylpentene with side chains)
first respond softly as the void space between polymer chains is compressed resisted
only by the relatively weak inter-molecular Van der Waals interaction. During this
phase, the covalent bonds of the polymer remain intact (Fig. 1.7). Once the voids
Another random document with
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use of the monks in their devotions. This summary of the first
contents of the library is taken by Hardy from the Gesta Abbatum, a
chronicle of St. Albans.
The literary interests of Paul were, it appears, continued by a large
proportion at least of his successors, and many of these made
important contributions to the library. Geoffrey, the sixteenth abbot,
gave to the scriptorium a missal bound in gold, and another missal in
two volumes, both incomparably illuminated in gold and written in an
open and legible script. He also gave a precious illuminated psalter,
a book containing the benediction and sacraments, a book of
exorcism, and a collectory. (The description is taken from the Gesta.)
Ralph, the seventeenth abbot, was said to have become a lover of
books after having heard Wodo of Italy expound the Scriptures. He
collected with diligence a large number of valuable manuscripts.
Robert de Gorham, who was called the reformer of the liberty of the
Church of St. Albans, after becoming prior, gave many books to the
scriptorium, more than could be mentioned by the author of the
Gesta. Simon, who became abbot in 1166, caused to be created the
office of historiographer. Simon had been educated in the abbey, and
did not a little to add to its fame as a centre of literature. He repaired
and enlarged the scriptorium, and he kept two or three scribes
constantly employed in it. The previous literary abbots had for the
most part brought from without the books added to the collection, but
it was under Simon that the abbey became a place of literary
production as well as of literary reproduction. He had an ordinance
enacted to the effect that every abbot must support out of his
personal funds one adequate scribe. Simon presented to the abbey
a considerable group of books that he had himself been collecting
before his appointment as abbot, together with a very beautiful copy
of the Old and New Testaments.
The next literary abbot was John de Cell, who had been educated
in the schools of Paris, and who was profoundly learned in grammar,
poetry, and physics. On being elected abbot, he gave over the
management of the temporal affairs of the abbey to his prior,
Reymond, and devoted himself to religious duties and to study.
Reymond himself was a zealous collector, and it was through him
that was secured for the library, among many other books, a copy of
the Historica Scholastica cum Allegoriis, of Peter Comester. The
exertions of these scholarly abbots and priors won for St. Albans a
special distinction among the monasteries of Britain, and naturally
led to the compilation of the historic annals which gave to the abbey
a continued literary fame. Hardy is of opinion that these historic
annals date from the administration of Simon, between the years
1166 and 1183.
Richard of Wendover, who succeeded Walter as historiographer,
compiled, between the years 1230 and 1236, the Flores Historiarum,
one of the most important of the earlier chronicles of England. Hardy
points out that it could have been possible to complete so great a
work within the term of six years, only on the assumption that
Richard found available much material collected by Walter, and it is
also probable that other compilations were utilised by Richard for the
work bearing his name. It is to be borne in mind that the monastic
chronicles were but seldom the production of a single hand, as was
the case with the chronicles of Malmesbury and of Beda. The greater
number of such chronicles grew up from period to period, fresh
material being added in succeeding generations, while in every
monastic house in which there were transcribers, fresh local
information was interpolated until the tributary streams had grown
more important than the original current. In this manner, the
monastic annals were at one time a transcript, at another time an
abridgment, and at another an original work. “With the chronicler,
plagiarism was no crime and no degradation. He epitomised or
curtailed or adapted the words of his predecessors in the same path
with or without alteration (and usually without acknowledgment),
whichever best suited his purpose or that of his monastery. He did
not work for himself but at the command of others, and thus it was
that a monastery chronicle grew, like a monastery house, at different
times, and by the labour of different hands.”
Of the heads that planned such chronicles or of the hands that
executed them, or of the exact proportion contributed by the several
writers, no satisfactory record has been preserved. The individual is
lost in the community.
In the earlier divisions of Wendover’s chronicle, covering the
centuries from 231 down to about 1000, Wendover certainly relied,
says Hardy, upon some previous compilation. About the year 1014,
that narrative, down to the death of Stephen, showed a marked
change in style, giving evidence that after this period some other
authority had been adopted, while there was also a larger
introduction of legendary matter. From the accession of Henry II., in
1235, when the Flores Historiarum ends, Wendover may be said to
assume the character of an original author. On the death of Richard,
the work of historiographer was taken up by Matthew Paris. His
Lives of the Two Offas and his famous Chronicles were produced
between the years 1236 and 1259.
In certain of the more literary of the English monasteries, the
divine offices were moderated in order to allow time for study, and,
under the regulations of some foundations, “lettered” persons were
entitled to special exemption from the performance of certain daily
services, and from church duty.[145]
At a visitation of the treasury of St. Pauls, made in the year 1295,
by Ralph de Baudoke, the Dean (afterwards Bishop of London),
there were found twelve copies of the Gospels adorned, some with
silver, and others with pearls and gems, and a thirteenth, the case
(capsa) containing which was decorated not merely with gilding but
with relics.[146] The treasury also contained a number of other
divisions of the Scriptures, together with a Commentary of Thomas
Aquinas. Maitland says that the use of relics as a decoration was an
unusual feature. He goes on to point out that the practice of using for
manuscripts a decorated case, caused the case, not infrequently, to
be more valuable than the manuscript itself, so that it would be
mentioned among the treasures of the church, when the book
contained in it was not sufficiently important to be even specified.
The binding of the books which were in general use in the English
monasteries for reference was usually in parchment or in plain
leather. The use of jewels, gold, or silver for the covers, or for the
capsæ, was, with rare exceptions, limited to the special copies
retained in the church treasury. William of Malmesbury in the
account which he gives of the chapel made at Glastonbury by King
Ina, mentions that twenty pounds and sixty marks of gold were used
in the preparation of the Coöpertoria Librorum Evangelii.[147]
The Earlier Monastery Schools.—At the time when
neither local nor national governments had assumed any
responsibilities in connection with elementary education, and when
the municipalities were too ignorant, and in many cases too poor, to
make provision for the education of the children, the monks took up
the task as a part of the regular routine of their duty. The Rule of S.
Benedict had in fact made express provision for the education of
pupils.
An exception to the general statement concerning the neglect of
the rulers to make provision for education should, however, be made
in the case of Charlemagne, whose reign covered the period 790 to
830. It was the aim of Charlemagne to correct or at least to lessen
the provincial differences and local barbarities of style, expression,
pression, orthography, etc., in the rendering of Latin, and it was with
this end in view that he planned out his great scheme of an imperial
series of schools, through which should be established an imperial or
academic standard of style and expression. This appears to have
been the first attempt since the time of the Academy of Alexandria to
secure a scholarly uniformity of the standard throughout the civilised
world, and the school at Tours may be considered as a precursor of
the French Academy of modern times. For such a scheme the
Emperor was dependent upon the monks, as it was only in the
monasteries that could be found the scholarship that was required
for the work. He entrusted to Alcuin, a scholarly English Benedictine,
the task of organising the imperial schools. The first schools
instituted by Alcuin in Aachen and Tours, and later in Milan, were
placed in charge of Benedictine monks, and formed the models for a
long series of monastic schools during the succeeding centuries.
Alcuin had been trained in the cathedral schools founded in York by
Egbert, and Egbert had been brought up by Benedict Biscop in the
monastery of Yarrow, where he had for friend and fellow pupil the
chronicler Bede. The results of the toilsome journeys taken by
Biscop to collect books for his beloved monasteries of Wearmouth
and Yarrow[148] were far-reaching. The training secured by Alcuin as
a scribe and as a student of the Scriptures, the classics, and the
“seven liberal arts” was more immediately due to his master Ælbert,
who afterward succeeded Egbert as archbishop.
The script which was accepted as the standard for the imperial
schools, and which, transmitted through successive Benedictine
scriptoria, served seven centuries later as a model for the first type-
founders of Italy and France, can be traced directly to the school at
York.
Alcuin commemorated his school and its master in a descriptive
poem On the Saints of the Church at York, which is quoted in full by
West.[149] In 780, Alcuin succeeded Ælbert as master of the school,
and later, was placed in charge of the cathedral library, which was at
the time one of the most important collections in Christendom. In one
of his poems he gives a kind of metrical summary of the chief
contents of this library. The lines are worth quoting because of the
information presented as to the authors at that time to be looked for
in a really great monastic library. The list includes a distinctive
though very restricted group of Latin writers, but, as West points out,
the works “by glorious Greece transferred to Rome” form but a
meagre group. The catalogue omits Isidore, although previous
references make clear that the writings of the great Spanish bishop
were important works of reference in York as in all the British
schools. It is West’s opinion that the Aristotle and other Greek
authors referred to were probably present only in Latin versions.
These manuscripts in the York library were undoubtedly for the most
part transcripts of the parchments collected for Wearmouth and
Yarrow by Biscop.
The Library of York Cathedral.
There shalt thou find the volumes that contain

All of the ancient Fathers who remain;
There all the Latin writers make their home
With those that glorious Greece transferred to Rome,
The Hebrews draw from their celestial stream,
And Africa is bright with learning’s beam.
Here shines what Jerome, Ambrose, Hilary thought,
Or Athanasius and Augustine wrought.
Orosius, Leo, Gregory the Great,
Near Basil and Fulgentius coruscate.
Grave Cassiodorus and John Chrysostom

Next Master Bede and learned Aldhelm come,
While Victorinus and Boëthius stand
With Pliny and Pompeius close at hand.
Wise Aristotle looks on Tully near,

Sedulius and Juvencus next appear.
Then come Albinus, Clement, Prosper too,
Paulinus and Arator. Next we view
Lactantius, Fortunatus. Ranged in line
Virgilius Maro, Statius, Lucan, shine.
Donatus, Priscian, Phobus, Phocas, start

The roll of masters in grammatic art.
Entychius, Servius, Pompey, each extend
The list. Comminian brings it to an end.
There shalt thou find, O reader, many more

Famed for their style, the masters of old lore,
Whose many volumes singly to rehearse
Were far too tedious for our present verse.[150]
Alcuin’s work on the Continent began in 782, when, resigning his

place as master of the cathedral school in York, he took charge of
the imperial or palace school at Tours. His work in the palace school
included not only the organisation of classes for the younger
students, but the personal charge of a class which comprised the
Emperor himself, his wife Luitgard, and other members of the royal
or imperial family. Whether for the younger or for the older students,
however, the instruction given had to be of a very elementary
character. The distinctive value of the work was, it is to be borne in
mind, not in the extent of the instruction given to the immediate
pupils, but in making clear to the Emperor and to his sons who were
to succeed him, the importance of securing a certain uniformity of
script and of educational work throughout the Empire.
It is very probable that not a few of the earlier copyists who
completed in the scriptoria the tasks set for them by the instructors
trained in Tours and in Aachen, transcribed texts the purport of which
they had not mastered. It was through their work, however, that the
texts themselves were preserved and were made available for later
scribes and students who were competent to comprehend the spirit
as well as the letter of their contents.
Mabillon is in accord with later authorities such as Compayré and
West, as to the deplorable condition of learning at this time
throughout the Empire ruled by Charles. Says West: “The plight of
learning in Frankland at this time was deplorable. Whatever
traditions had found their way from the early Gallic schools into the
education of the Franks had long since been scattered and
obliterated in the wild disorders which characterised the times of the
Merovingian kings.... The copying of books had almost ceased, and
all that can be found that pretends to the name of literature in this
time is the dull chronicle or ignorantly conceived legend.”[151]
A description such as this emphasises the importance of the work
initiated by Alcuin, work the value of which the ruler of Europe was
fortunately able to appreciate and ready to support. In his relation to
scholarly interests in Europe and to the preservation of the literature
of the past, Alcuin may fairly be considered as the successor of
Cassiodorus. He was able in the eighth century to render a service
hardly less distinctive than that credited to Cassiodorus three
hundred years earlier. There is the further parallel that, like
Cassiodorus, he possessed a very keen and intelligent interest in the
form given to literary expression, and in all the details of the work
given to the copyists. The instructions given in Alcuin’s treatise on
orthography for the work of the scribes, follow very closely in
principle, and differ, in fact, but slightly in detail from, the instructions
given by Cassiodorus in his own treatise on the same subject. A
couplet which stands at the head of the first page reads as follows:
“Let him who would publish the sayings of the ancients read me, for
he who follows me not will speak without regard to law.”[152] Alcuin’s
care in regard to the consistency of punctuation and orthography and
his intelligent selection of a clearer and neater form of script than
had heretofore been employed, have impressed a special character
on the series of manuscripts dating from the early portion of the ninth
century and written in what is termed the Caroline minuscule. In a
letter written to Charles from Tours in 799, Alcuin mentions that he
has copied out on some blank parchment which the King had sent
him a short treatise on correct diction, with illustrations from Bede.
He goes on to speak of the special value to literature of the
distinctions and subdistinctions of punctuation, the knowledge of
which has, he complains, almost disappeared: “But even as the glory
of all learning and the ornaments of wholesome erudition begin to be
seen again by reason of your noble exertions, so also it seems most
fitting that the use of punctuation should also be resumed by
scribes.... Let your authority so instruct the youths at the palace that
they may be able to utter with perfect elegance whatsoever the clear
eloquence of your thought may dictate, so that whatsoever may go
to the parchment bearing the royal name it may display the
excellence of the royal learning.”[153] A very delicate hint, remarks
West, for Charles to mind his commas and his colons.
Up to the time of Charlemagne there appears to have been so little
facility in writing and so few scribes were available, that government
records were not kept even at the Courts. The schools established
by Alcuin at Tours, under the direction of Charlemagne, were in fact
the first schools for writers which had existed in Western Europe for
centuries. One of the earlier applications made of the knowledge
gained in the imperial schools was for the critical analysis of certain
historical documents which had heretofore been accepted as final
authorities. In the earlier centuries of the Middle Ages, anything that
was in writing appears to have been accepted as necessarily
trustworthy and valuable, very much as in the earlier times of printing
the fact that a statement was in print caused it to be accepted as
something not to be contradicted. The critical faculty, combined with
the scholarly knowledge necessary and properly applied, was,
however, of slow growth, and centuries must still have passed
before, in this work of differentiating the value of documents, the
authority of scholars secured its full recognition.
After this work of Alcuin began, that is to say, after the beginning
of the ninth century, it became the rule of each properly organised
monastery to include, in addition to the scriptorium, an armarium, or
writing-chamber, which was utilised as a class-room for instruction in
writing and in Latin. In a letter of Canonicus Geoffrey, of St.-Barbe-
en-Auge, dated 1170, occurs the expression, Claustrum sine armario
est quasi castrum sine armamentario,[154] (a monastery without a
writing-chamber is like a camp without a storehouse of munitions or
an armory.)
The Capitular of Charlemagne, issued in the year 789, addressed
itself to the correction of the ignorance and carelessness of the
monks, and to the necessity of preserving a standard of correctness
for the work of transcribing holy writings. It contains the phrase:
Et pueros vestros non sinite eos vel legendo vel scribendo
corrumpere. Et si opus est evangelium, psalterium et missale
scribere, perfectæ ætatis homines scribant cum omni diligentia.
(Do not permit your pupils, either in reading or writing, to garble
the text;—and when you are preparing copies of the gospel, the
psalter, or the missal, see that the work is confided to men of mature
age, who will write with due care.)
The following lines were written by Alcuin as an injunction to pious
scribes:
AD MUSÆUM LIBROS SCRIBENTIUM.
Hic sedeant sacræ scribentes famina legis,

Nec non sanctorum dicta sacrata patrum.
His interserere caveant sua frivola verbis,
Frivola ne propter erret et ipsa manus,
Correctosque sibi quærant studiose libellos,
Tramite quo recto penna volantis eat.
Per cola distinguant proprios et commata sensus.
Et punctos ponant ordine quosque suo,
Ne vel falsa legat taceat vel forte repente,
Ante pios fratres lector in ecclesia.
.....
(Quoted from the Vienna Codex, 743. Denis, i., 313.)

Wattenbach is of opinion that these lines stood over the door of
the scriptorium of S. Martin’s Monastery.
West says that the lines were written as an injunction to the
scribes of the school at Tours. He gives the following version, which
takes in certain further lines of the original than those cited by
Wattenbach:
“Here let the scribes sit who copy out the words of the Divine Law,
and likewise the hallowed sayings of the holy Fathers. Let them
beware of interspersing their own frivolities in the words they copy,
nor let a trifler’s hand make mistakes through haste. Let them
earnestly seek out for themselves correctly written books to
transcribe, that the flying pen may speed along the right path. Let
them distinguish the proper sense by colons and commas, and let
them set the points each one in its due place, and let not him who
reads the words to them either read falsely or pause suddenly. It is a
noble work to write out holy books, nor shall the scribe fail of his due
reward. Writing books is better than planting vines, for he who plants
a vine serves his belly, but he who writes a book serves his
soul.”[155]
In a manuscript which was written in S. Jacob’s Monastery in
Liége, occurred the following lines:
Jacob Rebeccæ dilexit simplicitatem,

Altus mens Jacobi scribendi sedulitatem.
Ille pecus pascens se divitiis cumulavit,
Iste libros scribens meritum sibi multiplicavit.
Ille Rachel typicam præ cunctis duxit amatam,
Hic habeat vitam justis super astra paratam.[156]
[(The Hebrew) Jacob loved the simplicity of Rebecca,

The lofty soul of (the monk) Jacob (loved) the work of the
scribe.
The former accumulated riches in pasturing his flocks,
The latter increased his fame through the writing of books.
The former won his Rachel, loved beyond all others.
May the scribe have the eternal life which is prepared above
the stars for the just.]
The most important of the works of Alcuin that can be called

original were his educational writings, comprising treatises On
Grammar, On Orthography, On Rhetoric and the Virtues, On
Dialectics, A Disputation with Pepin, and a study of astronomy
entitled De Cursu et Saltu Lunæ ac Bissexto. West mentions three
other treatises which have been ascribed to him: On the Seven Arts,
A Disputation for Boys, and the Propositions of Alcuin.[157] Alcuin
was more fortunate than his great predecessor Cassiodorus in
respect to the preservation of his writings. Manuscripts of all of these
remained in existence until the time came when the complete set of
works could be issued in printed form, and the work of the old
instructor could be appreciated by a generation living a thousand
years after his life had closed. He died at Tours in 804, in his
seventieth year. Mabillon speaks of Alcuin as “the most learned man
of his age.” Laurie is disposed to lay stress upon the monastic
limitations of his intellect, and thinks that his principal ability was that
of an administrator; West emphasises the “pure unselfishness of his
character,” and adds, with discriminating appreciation: “We must also
credit him with a certain largeness of view, in spite of his
circumscribed horizon. He had some notion of the continuity of the
intellectual life of man, of the perils that beset the transmission of
learning from age to age, and of the disgrace which attached to
those who would allow those noble arts to perish which the wisest of
men among the ancients had discovered.... Perceiving that the
precious treasure of knowledge was then hidden in a few books, he
made it his care to transmit to future ages copies undisfigured by
slips of the pen or mistakes of the understanding. Thus in every way
that lay within his power, he endeavoured to put the fortunes of
learning for the times that should succeed him in a position of
advantage, safeguarded by an abundance of truthfully transcribed
books, interpreted by teachers of his own training, sheltered within
the Church and defended by the civil power.”[158] Professor West’s
appreciative summary does full justice to the work and the ideals of
Charlemagne’s great schoolmaster. I should only add that in the
special service he was in a position to render in the preservation,
transmission, and publication of the world’s literature, Alcuin must be
accorded a very high place in the series of literary workers which,
beginning with Cassiodorus, includes such names as Columba,
Biscop, Aurispa, Gutenberg, Aldus, Estienne, and Froben.
The most noteworthy of the successors of Alcuin in the palace
school at Tours was John Scotus Erigena, who in 845 was appointed
master by Charles the Bold. The influence of the Irish monk widened
the range of study and gave to it an active-minded and speculative
tendency that brought about a wide departure from the settled
conservatism which had always characterised the teaching of Alcuin.
The list of books given to the scribe for copying was increased, and
now included, for instance, works of such doubtful orthodoxy as the
Satyricon of Martianus Capella, a voluminous compilation
constituting a kind of cyclopædia of the seven liberal arts. Its
composition dates from about 500.[159]
In a treatise, De Instituto Clericorum, written in 819 (that is, during
the reign of Louis I.), by Rabanus Maurus, who was Abbot of Fulda
and later, Archbishop of Mayence, is cited the following regulation:
“The canons and the decrees of Pope Zosimus have decided that a
clerk proceeding to holy orders shall continue five years among the
readers ... and after that shall for four years serve as an acolyte or
sub-deacon.” (The Zosimus referred to was Pope for but one year,
417-418.) Rabanus had just before remarked, “Lectores are so
called a legendo.” He goes on to say that “he who would rightly and
properly perform the duty of a reader must be imbued with learning
and conversant with books, and must further be instructed in the
meaning of words and in the knowledge of the words themselves,”
etc.[160] Rabanus follows this with a series of very practical
instructions and suggestions for effective education on the part of the
readers. These were based upon the treatise on elocution written
nearly two hundred years earlier by the learned Bishop Isidore of
Seville, and they were again copied three years after the time of
Rabanus by Ibo, Bishop of Chartres, in the treatise De Rebus
Ecclesiasticis. Maitland, to whom I am indebted for this citation, finds
cause for indignant criticism of the historian Robertson for the
superficial and misleading references made by the historian to the
dense ignorance of the Church in the Middle Ages. Maitland
suggests that if Robertson had applied for holy orders to the
Archbishop of Seville in the seventh century, the Archbishop of
Mayence in the ninth, or the Bishop of Chartres in the eleventh, he
would have found the examination rather more of a task than he
expected. West speaks of Rabanus as “Alcuin’s greatest pupil,” and
as intellectually “a greater man than his master.”[161] He wrote a long
series of theological and educational treatises.
From the Constitutions of Reculfus, who became Bishop of
Soissons in 879, it is evident that he expected the clergy to be able
both to read and to write. The Bishop says: “We admonish that each
one of you should be careful to have a Missal, a Lectionary, a Book
of the Gospels, a Martyrology, an Antiphonary, a Psalter, and a copy
of the Forty Homilies of S. Gregory, corrected and pointed by our
copies which we use in the holy mother Church; and also fail not to
have as many sacred and ecclesiastical books as you can get, for
from these you shall receive food and condiment for your souls.... If,
however, any one of you is not able to obtain all the books of the Old
Testament, at least let him diligently take pains to transcribe for
himself correctly the first book of the whole sacred history, that is,
Genesis, by reading which he may come to understand the creation
of the world.”[162] The counsel was good, even although a perfectly
clear understanding of the creation might after all not have been
secured.
By the close of the ninth century, a large proportion of the
monasteries of the Continent and of England carried on schools
which were open to the children of as large a district as could be
reached. In many cases, the elementary classes were succeeded by
classes in advanced instruction, while from these were selected
favourites or exceptionally capable pupils, who enjoyed in still higher
studies the advantage of the guidance and service of the best
scholars in the monastery. West, in summing up the later influence of
Alcuin, speaks of the stream of learning as having flowed from York
to Tours and from Tours (through Rabanus) to Fulda, thence to
Auxerre, Ferrières, Corbies (old and new), Reichenau, St. Gall, and
Rheims, one branch of it finally reaching Paris.[163] Mabillon speaks
of the abbey schools of Fleury as containing during the tenth and
eleventh centuries as many as five thousand scholars.
In Italy, the most important schools were those instituted at Monte
Cassino, Pomposa, and Classe. Giesebrecht is, however, of opinion
that the educational work of the Italian monasteries was less
important than that carried on by the monasteries in Germany,
France, or England. In Germany, the monasteries which have
already been mentioned as centres of intellectual activity were also
those which had instituted the most important and effective of the
schools, the list including St. Gall, Fulda, Reichenau, Hirschau,
Wissembourg, Hersfeld, and many others.
In France and Belgium, the names of the conspicuous abbey
schools include those of Marmoutier, Fontenelle, Fleury, Corbie,
Ferrières, Bec, Clugni. In England, the most noteworthy of the abbey
schools were St. Albans, Glastonbury, Malmesbury, Croyland, and S.
Peter’s of Canterbury. From the epoch of Charlemagne to that of S.
Louis, the great abbeys of Christian Europe served in fact not only
as its schools but as its universities. The more intelligent of the
nobility and the kings themselves were interested in securing for
their children the educational advantages of the monastery schools.
Among the French kings who were brought up in this way are to be
named Pepin the Little, Robert the Pious, and Louis the Fat. In
Spain, Sancho the Great, King of Navarre and of Castile, was a
graduate of the monastery of Leyre.
In England, we have the noteworthy example of Alfred, who was
not ashamed, after having reached mature years, to repair his
imperfect education by attending the school established in Oxford by
the Benedictines, where he is said to have studied grammar,
philosophy, rhetoric, history, music, and versification.[164]
A large number of the convents, following the example of the
abbeys, contained schools in which were trained not only the future
novices, but also numbers of young girls destined for the life of the
Courts or of the world.
Mabillon finds occasion to correct the impression on the part of
some writers of the sixteenth century, that the monasteries had been
established solely for the purpose of carrying on educational work.
He writes: C’est une illusion de certains gens qui ont écrit dans le
siècle précédent que les monastères n’avaient esté d’abord établis
que pour servir d’écoles faisantes profession d’enseigner les
sciences humaines.
De Rancé, who wrote a Traité de la saincteté et du devoir de la vie
monastique, took the ground that the pursuit of literature was
inconsistent with the monastic profession, and that the reading of the
monks ought to be confined to the Scriptures and a few books of
devotion. The treatise was understood to be an attack upon the
Benedictine monks of St. Maur, for that they were learned was a
matter of general knowledge, and the monks of La Trappe, the Order
with which De Rancé had associated himself, had an old-time
antagonism to their scholarly neighbours. It may be considered as a
good service for literature and for monastic history that the treatise of
De Rancé, narrow and unimportant in itself as it was, should have
been published. Nine years later, in the year 1691, was issued the
reply of the Benedictines, the learned and valuable Traité des Études
Monastiques of Dom Mabillon, which will be referred to more
particularly in the following chapter.
The historians of these monastic schools have laid stress upon the
limited conceptions possessed by their founders and by the
instructors, of the purpose and possibilities of education, conceptions
which of necessity affected not only the work done in the school-
room, but the character of the literature produced in the scriptoria.
Laurie, for instance, writes as follows: “The Christian conception of
education was, unfortunately (like that of old Cato), narrow. It tended
steadily to concentrate and to contract men’s intellectual interests.
The Christian did not think of the culture of the whole man. He could
not consistently do so. His whole purpose was the salvation of the
soul.... Salvation was to be obtained through abnegation of the world
and through faith.... Christianity, accordingly, found itself necessarily
placed in mortal antagonism to ‘Humanitas’ and to Hellenism, and
had to go through the troublous experiences of nearly 1400 years
before the possibility of the union of reason with authority, of religion
with Hellenism, could be conserved.... As was indeed inevitable,
theological discussion more and more occupied the active intellect of
the time, to the subordination, if not total neglect of humane letters
and philosophy. The Latin and Greek classics were ultimately
denounced. As the offspring of the pagan world, if not indeed
inspired by demons, they were dangerous to the faith.”[165]
From the Apostolic Constitutions, ascribed to the middle of the
fourth century, Mr. Bass Mullinger quotes the injunction: “Refrain
from all the writings of the heathen: for what hast thou to do with
strange discourses, laws, or false prophets, which, in truth, turn
aside from the faith those who are weak in the understanding ...
wherefore abstain scrupulously from all strange and devilish
books.”[166]
It was S. Augustine who said Indocti cœlum rapiunt—“It is the
ignorant who take the kingdom of heaven,”—and Gregory the Great
who asserted that he would blush to have Holy Scripture subjected
to the rules of grammar.[167] West speaks of the conceptions of
grammar and of rhetoric taught by Alcuin as “crude” and “puerile,”
and of his theories of language as “childish.”
It is, of course, a truism to point out that the educational work done
by Alcuin and the other great instructors of the monastic schools is
not to be judged by the standard of later ages. The students for
whose training they were responsible, whether children or adults,
princes or peasants, must have been, with hardly an exception, in a
very elementary condition of mental development, and it was
necessary for the instruction to be in like manner elementary. In this
study, I am, however, not undertaking to consider the history of
education in early Europe, a subject which has been so ably
presented in the works of Mullinger, Laurie, Compayré, and West. I
am concerned with the work of these early schoolmasters simply
because to their persistent efforts was due the preservation of
literature in Europe. If Alcuin and his successors had done nothing
else than to secure a substantially uniform system of writing
throughout the great schools in which were trained abbots and
scribes for hundreds of monasteries, they would have conferred an
inestimable service upon Europe. But their work did go much further.
Notwithstanding the various injunctions and warnings of
ecclesiastical leaders against “pagan” literature, it proved
impracticable to prevent this literature from being preserved and
manifolded in numberless scriptoria. The record of the opposition
has been preserved in a series of edicts and injunctions. But the fact
that the interest in the writings of the ancients proved strong enough
to withstand all the fulminations and censures is evidenced by the
long series of manuscripts of the classics produced in the
monasteries during the tenth and eleventh centuries. The writers of
these manuscripts were the product of the schools instituted by
Charlemagne and Alcuin.
The Benedictines of the Continent.—The two writers
who have given the largest attention to the record of the literary and
scholarly work of the Benedictines during the seven centuries
between 500 and 1200 a.d., are Mabillon and Ziegelbauer. Dom
Mabillon was himself a Benedictine monk and had a full inheritance
of the literary spirit and scholarly devotion which characterised the
Order. He was born in Rheims in 1632, and his treatise on monastic
studies, Traité des Études Monastiques, which has remained the
chief authority on its subject, was published in Paris in 1691.
Ziegelbauer’s Observationes Literariæ S. Benedicti appeared a
century later.[168]
Mabillon’s work forms a magnificent monument not only to the
learning, diligence, and literary skill of its writer, but to the enormous
value of the services rendered, during a number of centuries, by the
monks of his Order, in the preservation of literature from the ravages
of barbarism and in the development of scholarship. Mabillon also
makes clear the lasting importance of the original initiative given to
the literary labour of the Benedictines by the Rule of their founder.
An important portion of the material upon which Mabillon’s treatise
was based, was collected during a series of journeys made by him in
company with his brother under the instructions first of the great
minister Colbert, and later, of Le Tellier, Archbishop of Rheims, for
the purpose of examining or of searching for documents relating to
the royal family and of procuring books for the royal library. The first
of these journeys, undertaken in the year 1682, was completed
entirely within French territory and was entitled Iter Burgundicum.
The second covered a considerable portion of South Germany and
Switzerland, and is known as the Iter Germanicum. The third was
devoted to Italy, and is described under the title of Iter Italicum; while
the fourth investigation was made in Alsace and Lorraine, and the
record is entitled Iter Literarium in Alsatiam et Lotharingiam.
The plan of the journeys involved a thorough ransacking of as
many libraries as they could secure admission to, the libraries being,
with but few exceptions, contained in the monasteries. The
immediate result of these journeys was the addition to the royal
library of some three thousand volumes, chiefly collected in Italy, and
the later result, the publication of the records above specified, which
form a most valuable presentation of the condition of the monastic
collections in the seventeenth century, and which give in their lists
the titles of a considerable number of valuable works which have
since entirely disappeared.
A century later than S. Benedict, an unknown hermit called “the
Master” prepared a Rule under which monks were required to study
until they reached the age of fifty.[169] The Rule of S. Aurelian and S.
Ferreol rendered this regulation universal, and that of Grimlaïcus
identified the character of the hermit with that of “doctor.”[170] In all
countries where the Benedictine Orders flourished, literature and
scholarship exercised an abiding influence. It is impossible, contends
Montalembert, to name an abbey famed for the number and holiness
of its monks which is not also noted for learning and for its school of
literature. The Benedictine monks during the four or five centuries
after the foundation of the Order certainly appear to have held
themselves faithful to the precept of S. Jerome, “A book always in
your hand or under your eyes.” (Nunquam de manu necque oculis
recedat liber.[171]) They also accepted very generally the example of
Bede, who said that it had been for him always delightful either to
learn, to teach, or to write.[172] Warton is authority for the statement
that in the year 790 Charlemagne granted to the abbot and monks of
Sithiu an unlimited right of hunting, in order that they might procure
from the skins of the deer killed, gloves, girdles, and covers for their
books. He goes on to say: “We may imagine that these religious
were more fond of hunting than of reading. It is certain that they were
obliged to hunt before they could read, and it seems probable that
under these circumstances they did not manufacture many
volumes.”[173] Maitland, in referring to the original text of the
concession, finds, however, that this has been misread by Warton.
The permission to hunt, for the useful purpose specified, was given
not for the monks but for the servants of the monastery.
With all the great Benedictine monasteries, it was the routine to
institute first a library, then a scriptorium for the manifolding of books,
and finally schools, open, not only to students who were preparing
for the Church, but to all in the neighbourhood who had need of or
desire for instruction. The copies prepared in the scriptorium of the
texts from the library were utilised in the first place for the duplicates
needed of the works in most frequent reference, but more
particularly for securing by exchange copies of texts not already in
the library, and, in many instances, also for adding either to the direct
wealth of the monastery (by exchange for lands or cattle) or to its
income by making sale of the works through travelling monks or by
correspondence with other monasteries.
The list of monasteries which became in this manner literary and
publishing centres would include nearly all the great Benedictine
foundations of both Britain and the Continent. There was probably,
however, a greater activity during the period between 600 and 1200,
in the matter at least of collecting and circulating books, in the
monasteries of France than in those of Italy, Germany, or Britain; but
more important even than Clugni, Marmoutier, or Corbie, in France,
was the great Swiss abbey of St. Gall, an abbey the realm of which
reached almost to the proportions of a small municipality. In the
shade of its walls, there dwelt a whole nation, divided into two
branches, the familia intus, which comprised the labourers,
shepherds, and workmen of all trades, and the familia foris,
composed of serfs, who were bound to do three days’ work in each
week.
Within the monastery itself, there were, in the latter half of the
tenth century, no less than five hundred monks, together with a great
group of students. In Germany, the most noted of what might be
called the literary monasteries during the ninth and tenth centuries
were those of Fulda, Reichenau, Lorsch, Hirschau, and
Gandersheim. It was in the latter that the nun Hroswitha composed
her famous dramas. In France, in addition to those already specified,
should be mentioned Fleury, St. Remy, St. Denis, Luxeuil, S. Vincent
at Toul, and Aurillac. In Belgium, S. Peter’s at Ghent was, during the
tenth century, the most important of the scholarly monasteries. In
England, in addition to the earlier foundations, already referred to, of
Wearmouth and Yarrow, St. Albans and Glastonbury became the
most famous. Before the eleventh century, the literature that came
into existence from contemporary writers or reproductions of the
works of classic writers outside of the monasteries must have been
very trifling indeed. One of the most noteworthy publications which
emanated from St. Gall was the great dictionary or Vocabulary
bearing the name of Solomon (Abbot of St. Gall and later, Bishop of
Constance), a work which was in fact a kind of literary and scientific
encyclopædia. This manuscript, comprising in all 1070 pages, was
put into print in the latter part of the fifteenth century.[174] The
records of the famous library of the monastery have been brought
together by later scholars, and it is their testimony that the
manuscripts contained in it were among the most beautiful and
accurate specimens of caligraphy known. These St. Gall
manuscripts were also noted for their exquisite miniatures and
illuminations. The parchment used for them was prepared by the
hands of the monks, and they also did their own binding.[175] The
fame of Sintram, one of the most noteworthy of the copyists, was

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Computational Approaches for

Chemistry Under Extreme Conditions

Constitutionalism Under Extreme Conditions: Law,

Nonlinear dynamics of structures under extreme

Cell Biology and Translational Medicine Volume 2

Indistractable Nir Eyal

Foundations of High Energy Density Physics Physical

Quantum Computational Chemistry Modelling and

Team Coordination in Extreme Environments Work

Computational Approaches for Studying Enzyme Mechanism

Nir Goldman Editor

More information about this series at http://www.springer.com/series/6918

ISSN 2542-4491 ISSN 2542-4483 (electronic)

Library of Congress Control Number: 2018964691

© Springer Nature Switzerland AG 2019

Livermore, USA Nir Goldman

1 Simulations of Hydrocarbon Polymers Related to Compression

9 Data-Driven Methods for Building Reduced Kinetic Monte

Thomas R. Mattsson, Kyle R. Cochrane, J. Matthew D. Lane and Seth Root

Abstract High-fidelity modeling of hydrocarbon polymers is important for gaining

Hydrocarbon polymers are versatile and therefore ubiquitous materials in experimen-

T. R. Mattsson (B) · K. R. Cochrane · J. M. D. Lane · S. Root

© Springer Nature Switzerland AG 2019 1

1.2 First-Principles Simulations of Shocked Polymers

First-principles simulations using Density Functional Theory have brought important

1.2.1 First-Principles Thermodynamics of Shock

DFT is applied to problems in physics, material science, and chemistry to calculate

(P2 − P1 ) ρ1 (u s − u 1 )(u 2 − u 1 ) (1.1)

ρ2/ ρ1 (u s − u 1 )/(u s − u 2 ) (1.2)

In thermodynamic space, the loci of end states generated from successively

plane-wave cutoff energies, finite-temperature DFT using many partially occupied

1.2.2 Analysis of Chemical Composition—Tracking Bonds

Of particular importance to simulation of polymers compared to elements is the pres-

Tracking bonds in a simulation is a three-step process. We determine bond lengths,

Fig. 1.5 Species-dependent

1.3 Classical Molecular Dynamics Simulations of Polymers

DFT allows extremely high-fidelity descriptions of chemistry over a huge range of

nificantly address the observed shortcomings in their high compression response.

1.4 Z Experiments on Polymer Materials

B 2 (t) J 2 (t) μ0 I 2 (t)

Fig. 1.17 Analysis of the

1.5 Summary and Conclusions

There shalt thou find the volumes that contain

Grave Cassiodorus and John Chrysostom

Wise Aristotle looks on Tully near,

Donatus, Priscian, Phobus, Phocas, start

There shalt thou find, O reader, many more

Alcuin’s work on the Continent began in 782, when, resigning his

Hic sedeant sacræ scribentes famina legis,

(Quoted from the Vienna Codex, 743. Denis, i., 313.)

Jacob Rebeccæ dilexit simplicitatem,

[(The Hebrew) Jacob loved the simplicity of Rebecca,

The most important of the works of Alcuin that can be called

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